1508
G.-L. QIU ET AL.
2.3.1. 7,9-Dichloro-2-methyl-1,10b-dihydro-5H-pyrazolo[1,5-c][1,3] 2.3.6. 9-Chloro-2-methyl-1,10b-dihydro-5H-pyrazolo[1,5-c][1,3]ben-
benzoxazin-5-one (6a) zoxazin-5-thione (6f)
White powder, yield: 27%; m.p. 237–240 ꢁC; 1H NMR (300 MHz, Light yellow powder, yield: 28%; m.p. 220–222 ꢁC; 1H NMR
CDCl3) d 7.42 (d, J ¼ 2.2 Hz, 1H, Ar[sbond]H), 7.03 (d, J ¼ 1.2 Hz, 1H, (300 MHz, CDCl3) d 7.35 (dd, J ¼ 8.7, 2.0 Hz, 1H, Ar[sbond]H), 7.18
Ar[sbond]H), 5.31–5.20 (m, 1H, 10b-H), 3.35 (dd, J ¼ 16.8, 10.3 Hz, (d, J ¼ 8.7 Hz, 1H, Ar[sbond]H), 7.12 (d, J ¼ 1.3 Hz, 1H, Ar[sbond]H),
1H, 1-Ha), 3.11 (dd, J ¼ 16.7, 12.7 Hz, 1H, 1-Hb), 2.20 (s, 3H, CH3); 5.28–5.12 (m, 1H, 10b-H), 3.49 (dd, J ¼ 17.1, 10.0 Hz, 1H, 1-Ha), 3.21
13C NMR (75 MHz, CDCl3) d 160.3 (C[dbond]O), 145.4 (C[dbond]N), (dd, J ¼ 17.5, 12.5 Hz, 1H, 1-Hb), 2.29 (s, 3H, CH3); 13C NMR
145.1 (C[sbond]O), 130.3, 130.1, 125.5, 123.34, 123.30, 57.2 (C-10b), (75 MHz, CDCl3) d 176.1 (C[dbond]S), 164.7 (C[dbond]N), 148.3
42.4 (C-1), 16.4 (CH3). TOF-HRMS: m/z [M þ H]þ calcd for (C[sbond]O), 130.9, 130.2, 124.7, 123.5, 118.0, 57.3 (C-10b), 42.9 (C-
C11H9Cl2N2O2: 271.0036; found: 271.0038.
1), 16.8 (CH3). TOF-HRMS: m/z [M þ H]þ calcd for C11H10ClN2OS:
253.0197; found: 253.0201.
2.3.2. 7,9-Dichloro-2-methyl-1,10b-dihydro-5H-pyrazolo[1,5-c][1,3]
benzoxazin-5-thione (6b)
2.3.7. 9-Bromo-2-methyl-1,10b-dihydro-5H-pyrazolo[1,5-c][1,3]ben-
zoxazin-5-one (6g)
White powder, yield: 35%; m.p. 230–233 ꢁC; 1H NMR (300 MHz,
White powder, yield: 27%; m.p. 211–213 ꢁC; 1H NMR (300 MHz,
CDCl3) d 7.46 (dd, J ¼ 8.7, 1.7 Hz, 1H, Ar[sbond]H), 7.27–7.25 (m,
1H, Ar[sbond]H), 7.04 (d, J ¼ 8.7 Hz, 1H, Ar[sbond]H), 5.24 (dd,
J ¼ 12.6, 10.4 Hz, 1H, 10b-H), 3.33 (dd, J ¼ 16.8, 10.3 Hz, 1H, 1-Ha),
3.11 (dd, J ¼ 17.9, 12.7 Hz, 1H, 1-Hb), 2.18 (d, J ¼ 6.2 Hz, 3H, CH3);
13C NMR (75 MHz, CDCl3) d 159.8 (C[dbond]O), 149.6 (C[dbond]N),
146.0 (C[sbond]O), 132.9, 127.8, 124.8, 118.9, 117.5, 56.9 (C-10b),
42.5 (C-1), 16.4 (CH3). TOF-HRMS: m/z [M þ H]þ calcd for
C11H10BrN2O2: 280.9920; found: 280.9925.
CDCl3)
d
7.43 (d, J ¼ 1.7 Hz, 1H, Ar[sbond]H), 7.04 (s, 1H,
Ar[sbond]H), 5.25 (t, J ¼ 10.9 Hz, 1H, 10b-H), 3.51 (dd, J ¼ 17.1,
10.1 Hz, 1H, 1-Ha), 3.22 (dd, J ¼ 17.0, 11.9 Hz, 1H, 1-Hb), 2.29 (s, 3H,
CH3); 13C NMR (75 MHz, CDCl3)
d 174.8 (C[dbond]S), 164.7
(C[dbond]N), 144.6 (C[sbond]O), 130.7, 130.4, 124.8, 123.0, 122.7,
57.4 (C-10b), 42.7 (C-1), 16.7 (CH3).TOF-HRMS: m/z [M þ H]þ calcd
for C11H9Cl2N2OS: 286.9807; found: 286.9806.
2.3.3. 7,9-Dibromo-2-methyl-1,10b-dihydro-5H-pyrazolo[1,5-c][1,3]
benzoxazin-5-one (6c)
2.3.8. 9-Bromo-2-methyl-1,10b-dihydro-5H-pyrazolo[1,5-c][1,3]ben-
zoxazin-5-thione (6h)
White powder, yield: 30%; m.p. 229–232 ꢁC; 1H NMR (300 MHz,
CDCl3) d 7.81–7.67 (m, 1H, Ar[sbond]H), 7.21 (dd, J ¼ 2.1, 1.1 Hz, Light yellow powder, yield: 31%; m.p. 245–247 ꢁC; 1H NMR
1H, Ar[sbond]H), 5.26 (dd, J ¼ 12.5, 10.4 Hz, 1H, 10b-H), 3.35 (dd, (300 MHz, CDCl3) d 7.50 (dd, J ¼ 8.7, 1.8 Hz, 1H, Ar[sbond]H),
J ¼ 16.9, 10.3 Hz, 1H, 1-Ha), 3.12 (dd, J ¼ 16.8, 12.6 Hz, 1H, 1-Hb), 7.27–7.25 (m, 1H, Ar[sbond]H), 7.14 (d, J ¼ 8.7 Hz, 1H, Ar[sbond]H),
2.20 (s, 3H, CH3); 13C NMR (75 MHz, CDCl3) d 160.3 (C[dbond]O), 5.26–5.11 (m, 1H, 10b-H), 3.47 (dd, J ¼ 17.1, 10.0 Hz, 1H, 1-Ha), 3.21
147.1 (C[dbond]N), 145.1 (C[sbond]O), 135.9, 126.88, 125.8, 117.5, (dd, J ¼ 18.1, 12.0 Hz, 1H, 1-Hb), 2.29 (s, 3H, CH3); 13C NMR
112.0, 57.1 (C-10b), 42.4 (C-1), 16.4 (CH3). TOF-HRMS: m/z [M þ H]þ (75 MHz, CDCl3) d 176.0 (C[dbond]S), 164.2 (C[dbond]N), 148.7
calcd for C11H9Br2N2O2: 358.9025; found: 358.9023.
(C[sbond]O), 133.1, 127.5, 123.7, 118.3, 118.1, 57.0 (C-10b), 42.8 (C-
1), 16.7 (CH3). TOF-HRMS: m/z [M þ H]þ calcd for C11H10BrN2OS:
296.9692; found: 296.9695.
2.3.4. 7,9-Dibromo-2-methyl-1,10b-dihydro-5H-pyrazolo[1,5-c][1,3]
benzoxazin-5-thione (6d)
2.3.9. 7-Bromo-9-chloro-2-methyl-1,10b-dihydro-5H-pyrazolo[1,5-c]
[1,3]benzoxazin-5-one (6i)
White powder, yield, 26%; m.p. 268–270 ꢁC; 1H NMR (300 MHz,
CDCl3) d 7.76 (d, J ¼ 1.7 Hz, 1H, Ar[sbond]H), 7.21 (d, J ¼ 0.8 Hz, 1H,
Ar[sbond]H), 5.25–5.15 (m, 1H, 10b-H), 3.47 (dd, J ¼ 17.1, 10.0 Hz,
1H, 1-Hb), 3.21 (dd, J ¼ 16.2, 11.9 Hz, 1H, 1-Hb), 2.29 (s, 3H,
White powder, yield: 29%; m.p. 228–231 ꢁC; 1H NMR (300 MHz,
CDCl3)
d
7.59 (d, J ¼ 2.2 Hz, 1H, Ar[sbond]H), 7.07 (s, 1H,
Ar[sbond]H), 5.31–5.20 (m, 1H, 10b-H), 3.34 (dd, J ¼ 16.8, 10.3 Hz,
CH3).13C NMR (75 MHz, CDCl3)
d 175.1 (C[dbond]S), 164.5
1H, 1-Ha), 3.11 (dd, J ¼ 16.3, 12.8 Hz, 1H, 1-Hb), 2.20 (s, 3H, CH3);
(C[dbond]N), 146.6 (C[sbond]O), 136.3, 126.7, 125.1, 118.2, 111.6,
57.5 (C-10b), 42.9 (C-1), 16.9 (CH3). TOF-HRMS: m/z [M þ H]þ calcd
for C11H9Br2N2OS: 376.8776; found: 376.8777.
13C NMR (75 MHz, CDCl3)
d
160.13 (C[dbond]O), 146.66
(C[dbond]N), 145.15 (C[sbond]O), 133.3, 130.5, 125.3, 123.9, 111.8,
57.2 (C-10b), 42.4 (C-1), 16.4 (CH3). TOF-HRMS: m/z [M þ H]þ calcd
for C11H9BrClN2O2: 314.9530; found: 314.9537.
2.3.5. 9-Chloro-2-methyl-1,10b-dihydro-5H-pyrazolo[1,5-c][1,3]ben-
zoxazin-5-one (6e)
2.3.10. 7-Bromo-9-chloro-2-methyl-1,10b-dihydro-5H-pyrazolo[1,5-
c][1,3]benzoxazin-5-thione (6j)
White powder, yield: 32%; m.p. 184–186 ꢁC; 1H NMR (300 MHz,
CDCl3) d 7.31 (dd, J ¼ 8.7, 2.4 Hz, 1H, Ar[sbond]H), 7.12 (dd, J ¼ 2.4, White powder, yield: 30%; m.p. 248–250 ꢁC; 1H NMR (300 MHz,
1.0 Hz, 1H, Ar[sbond]H), 7.09 (d, J ¼ 8.8 Hz, 1H, Ar[sbond]H), 5.24 CDCl3) d 7.60 (d, J ¼ 2.1 Hz, 1H, Ar[sbond]H), 7.07 (d, J ¼ 1.1 Hz, 1H,
(dd, J ¼ 12.6, 10.4 Hz, 1H, 10b-H), 3.34 (dd, J ¼ 16.8, 10.3 Hz, 1H, 1- Ar[sbond]H), 5.23 (t, J ¼ 10.9 Hz, 1H, 10b-H), 3.49 (dd, J ¼ 17.1,
Ha), 3.11 (dd, J ¼ 17.9, 12.7 Hz, 1H, 1-Hb), 2.19 (s, 3H, CH3); 13C 10.1 Hz, 1H, 1-Ha), 3.21 (dd, J ¼ 16.7, 12.2 Hz, 1H, 1-Hb), 2.29 (s, 3H,
NMR (75 MHz, CDCl3) d 159.9 (C[dbond]O), 149.1 (C[dbond]N), CH3); 13C NMR (75 MHz, CDCl3)
d 175.0 (C[dbond]O), 165.0
146.1 (C[sbond]O), 130.2, 129.9, 124.9, 124.3, 118.5, 57.0 (C-10b), (C[dbond]N), 146.0 (C[sbond]O), 133.4, 131.1, 124.7, 123.9, 111.1,
42.5 (C-1), 16.4 (CH3). TOF-HRMS: m/z [M þ H]þ calcd for 57.6 (C-10b), 42.8 (C-1), 16.9 (CH3). TOF-HRMS: m/z [M þ H]þ calcd
C11H10ClN2O2: 237.0425; found: 237.0430.
for C11H9BrClN2OS: 330.9302; found: 330.9306.